1,4-Bis(2-pyridylimino­meth­yl)benzene

Huo, L.-H.; Gao, S.; Ng, S.W.

doi:10.1107/S1600536809039853

organic compounds

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ISSN: 2056-9890

Volume 65| Part 11| November 2009| Page o2659

https://doi.org/10.1107/S1600536809039853

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1,4-Bis(2-pyridyliminomethyl)benzene

Li-Hua Huo,^a Shan Gao ^a and Seik Weng Ng ^b ^*

^aCollege of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, People's Republic of China, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 28 September 2009; accepted 30 September 2009; online 7 October 2009)

In the crystal structure of the title compound, C₁₈H₁₄N₄, the molecule assumes $[\overline{1}]$ site symmetry with the centroid of the benzene ring located on the inversion center. The molecule is almost flat, with a dihedral angle of 2.70 (9)° between the pyridine and benzene rings.

Related literature

For the synthesis, see: D'Alelio et al. (1967 ). Terephthaldehyde condenses directly with 2-aminopyridine to form 4-(bis(2-pyridylamino)methyl)benzaldehyde; see: Zhu et al. (2003 ).

Experimental

Crystal data

C₁₈H₁₄N₄
M_r = 286.33
Monoclinic, P 2₁ /n
a = 6.1579 (8) Å
b = 18.911 (3) Å
c = 6.5956 (11) Å
β = 109.746 (5)°
V = 722.90 (18) Å³
Z = 2
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 293 K
0.30 × 0.26 × 0.21 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.976, T_max = 0.983
7013 measured reflections
1657 independent reflections
886 reflections with I > 2σ(I)
R_int = 0.048

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.168
S = 1.05
1657 reflections
100 parameters
H-atom parameters constrained
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalClear (Rigaku/MSC, 2002 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536809039853/xu2625sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809039853/xu2625Isup2.hkl

checkCIF report

Related literature top

For the synthesis, see: D'Alelio et al. (1967). Terephthaldehyde condenses directly with 2-aminopyridine to form 4-(bis(2-pyridylamino)methyl)benzaldehyde; see: Zhu et al. (2003).

Experimental top

To a solution of terephthaladehyde (1 mmol) in methanol was added a solution of 2-aminopyridine (2 mmol) and cobalt acetate trihydrate (1 mmol) in methanol. The mixture was heated to 333 K for one hour. The pale yellow solution was filtered. Colorless crystals were isolated from the filtrate after several days. CH&N elemental analysis. Calc. for C₁₈H₁₄N₄: C 75.51, H 4.93, N 19.57%; found: C 75.53, H 4.98, N 19.53%.

Structure description top

For the synthesis, see: D'Alelio et al. (1967). Terephthaldehyde condenses directly with 2-aminopyridine to form 4-(bis(2-pyridylamino)methyl)benzaldehyde; see: Zhu et al. (2003).

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalClear (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of the title compound at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

1,4-Bis(2-pyridyliminomethyl)benzene top

Crystal data top

C₁₈H₁₄N₄	F(000) = 300
M_r = 286.33	D_x = 1.315 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3577 reflections
a = 6.1579 (8) Å	θ = 3.5–27.5°
b = 18.911 (3) Å	µ = 0.08 mm⁻¹
c = 6.5956 (11) Å	T = 293 K
β = 109.746 (5)°	Prism, colorless
V = 722.90 (18) Å³	0.30 × 0.26 × 0.21 mm
Z = 2

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	1657 independent reflections
Radiation source: fine-focus sealed tube	886 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.048
ω scans	θ_max = 27.5°, θ_min = 3.5°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −7→7
T_min = 0.976, T_max = 0.983	k = −24→24
7013 measured reflections	l = −8→8

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.168	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0811P)² + 0.0419P] where P = (F_o² + 2F_c²)/3
1657 reflections	(Δ/σ)_max = 0.001
100 parameters	Δρ_max = 0.15 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₈H₁₄N₄	V = 722.90 (18) Å³
M_r = 286.33	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.1579 (8) Å	µ = 0.08 mm⁻¹
b = 18.911 (3) Å	T = 293 K
c = 6.5956 (11) Å	0.30 × 0.26 × 0.21 mm
β = 109.746 (5)°

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	1657 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	886 reflections with I > 2σ(I)
T_min = 0.976, T_max = 0.983	R_int = 0.048
7013 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.168	H-atom parameters constrained
S = 1.05	Δρ_max = 0.15 e Å⁻³
1657 reflections	Δρ_min = −0.21 e Å⁻³
100 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.2738 (3)	0.57623 (8)	0.4070 (3)	0.0484 (5)
N2	0.4005 (3)	0.67692 (8)	0.6348 (3)	0.0547 (5)
C1	0.3212 (3)	0.48484 (9)	0.0748 (3)	0.0490 (5)
H1	0.2001	0.4745	0.1242	0.059*
C2	0.6436 (3)	0.55629 (10)	0.0822 (3)	0.0501 (6)
H2	0.7408	0.5945	0.1371	0.060*
C3	0.4653 (3)	0.54201 (9)	0.1610 (3)	0.0422 (5)
C4	0.4303 (3)	0.58674 (9)	0.3268 (3)	0.0470 (5)
H4	0.5285	0.6251	0.3762	0.056*
C5	0.2518 (3)	0.62320 (9)	0.5657 (3)	0.0427 (5)
C6	0.0719 (4)	0.61176 (10)	0.6427 (3)	0.0505 (6)
H6	−0.0267	0.5735	0.5940	0.061*
C7	0.0405 (4)	0.65755 (10)	0.7920 (3)	0.0566 (6)
H7	−0.0817	0.6513	0.8431	0.068*
C8	0.1919 (4)	0.71275 (11)	0.8649 (4)	0.0585 (6)
H8	0.1762	0.7443	0.9673	0.070*
C9	0.3676 (4)	0.71989 (10)	0.7815 (4)	0.0598 (6)
H9	0.4701	0.7572	0.8310	0.072*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0544 (10)	0.0491 (9)	0.0460 (11)	−0.0014 (8)	0.0225 (9)	−0.0062 (7)
N2	0.0572 (11)	0.0523 (10)	0.0595 (12)	−0.0048 (8)	0.0260 (9)	−0.0111 (8)
C1	0.0530 (12)	0.0510 (11)	0.0503 (13)	−0.0033 (9)	0.0268 (10)	−0.0034 (9)
C2	0.0523 (12)	0.0492 (11)	0.0540 (13)	−0.0120 (9)	0.0250 (11)	−0.0078 (9)
C3	0.0472 (11)	0.0413 (10)	0.0389 (11)	0.0030 (8)	0.0158 (9)	0.0011 (8)
C4	0.0505 (12)	0.0453 (11)	0.0478 (13)	−0.0031 (9)	0.0202 (10)	−0.0036 (9)
C5	0.0452 (11)	0.0419 (10)	0.0415 (11)	0.0036 (8)	0.0156 (9)	0.0002 (8)
C6	0.0544 (13)	0.0496 (11)	0.0531 (14)	−0.0030 (9)	0.0256 (11)	−0.0022 (9)
C7	0.0674 (14)	0.0548 (12)	0.0588 (14)	0.0064 (10)	0.0361 (12)	0.0009 (10)
C8	0.0741 (14)	0.0513 (12)	0.0564 (14)	0.0079 (11)	0.0305 (12)	−0.0071 (10)
C9	0.0673 (14)	0.0500 (11)	0.0639 (15)	−0.0090 (10)	0.0247 (12)	−0.0159 (10)

Geometric parameters (Å, º) top

N1—C4	1.262 (2)	C3—C4	1.455 (3)
N1—C5	1.414 (2)	C4—H4	0.9300
N2—C9	1.330 (2)	C5—C6	1.383 (3)
N2—C5	1.340 (2)	C6—C7	1.373 (3)
C1—C2ⁱ	1.369 (3)	C6—H6	0.9300
C1—C3	1.392 (3)	C7—C8	1.374 (3)
C1—H1	0.9300	C7—H7	0.9300
C2—C1ⁱ	1.369 (3)	C8—C9	1.376 (3)
C2—C3	1.391 (3)	C8—H8	0.9300
C2—H2	0.9300	C9—H9	0.9300

C4—N1—C5	119.30 (17)	N2—C5—N1	120.16 (16)
C9—N2—C5	117.11 (17)	C6—C5—N1	117.58 (17)
C2ⁱ—C1—C3	120.54 (17)	C7—C6—C5	119.28 (19)
C2ⁱ—C1—H1	119.7	C7—C6—H6	120.4
C3—C1—H1	119.7	C5—C6—H6	120.4
C1ⁱ—C2—C3	121.24 (17)	C6—C7—C8	119.14 (19)
C1ⁱ—C2—H2	119.4	C6—C7—H7	120.4
C3—C2—H2	119.4	C8—C7—H7	120.4
C2—C3—C1	118.21 (17)	C7—C8—C9	117.83 (19)
C2—C3—C4	120.26 (17)	C7—C8—H8	121.1
C1—C3—C4	121.52 (16)	C9—C8—H8	121.1
N1—C4—C3	123.46 (18)	N2—C9—C8	124.36 (19)
N1—C4—H4	118.3	N2—C9—H9	117.8
C3—C4—H4	118.3	C8—C9—H9	117.8
N2—C5—C6	122.26 (17)

C1ⁱ—C2—C3—C1	−0.5 (3)	C4—N1—C5—N2	−2.1 (3)
C1ⁱ—C2—C3—C4	−179.58 (18)	C4—N1—C5—C6	177.18 (19)
C2ⁱ—C1—C3—C2	0.5 (3)	N2—C5—C6—C7	1.3 (3)
C2ⁱ—C1—C3—C4	179.57 (18)	N1—C5—C6—C7	−177.98 (17)
C5—N1—C4—C3	−179.24 (17)	C5—C6—C7—C8	−1.5 (3)
C2—C3—C4—N1	−179.11 (19)	C6—C7—C8—C9	0.8 (3)
C1—C3—C4—N1	1.9 (3)	C5—N2—C9—C8	−0.2 (3)
C9—N2—C5—C6	−0.5 (3)	C7—C8—C9—N2	0.1 (4)
C9—N2—C5—N1	178.83 (18)

Symmetry code: (i) −x+1, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₁₈H₁₄N₄
M_r	286.33
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	6.1579 (8), 18.911 (3), 6.5956 (11)
β (°)	109.746 (5)
V (Å³)	722.90 (18)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.30 × 0.26 × 0.21

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.976, 0.983
No. of measured, independent and observed [I > 2σ(I)] reflections	7013, 1657, 886
R_int	0.048
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.168, 1.05
No. of reflections	1657
No. of parameters	100
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.21

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalClear (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2009).

Acknowledgements

We thank the Natural Science Foundation of Heilongjiang Province (No. B200501), Heilongjiang University, China, and the University of Malaya for supporting this study.

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
D'Alelio, G. F., Crivello, J. V., Schönig, R. K. & Hümmer, T. F. (1967). J. Macromol. Sci. Chem. 1, 1251–1258. CrossRef CAS Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
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Rigaku/MSC (2002). CrystalClear. Rigaku/MSC Inc., The Woodlands, Texas, USA. Google Scholar
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